US20200354651A1

US20200354651A1 - Hard surface cleaning compositions comprising alkoxylated phenols and perfumes and cleaning pads and methods for using such cleaning compositions

Info

Publication number: US20200354651A1
Application number: US16/868,714
Authority: US
Inventors: Fernando Ray Tollens; Pauline Cuc Vu; Brian Christopher Groendyke; William Alexander CYNECKI; Daniel Ross MAYFIELD; Afua Sarpong KARIKARI
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2019-05-10
Filing date: 2020-05-07
Publication date: 2020-11-12
Also published as: EP3966305A1; JP7375041B2; JP2022530943A; CA3139842A1; WO2020232464A1

Abstract

A hard surface cleaning composition, methods of improving the shine and reducing malodour on a hard surface and disposable premoistened pads for cleaning hard surfaces with controlled emulsification is provided. The hard surface cleaning composition comprises: at least 85% by weight of water; at least 0.0015% of by weight of alkoxylated phenol; and a perfume. The perfume comprises at least 60% by weight of the Perfume Raw Materials having C log P greater than 1.0. The composition has a Shine Result of between 0.1 and 2.0 and an NTU of between 1 and 200.

Description

FIELD

The present disclosure is generally directed to a hard surface cleaning composition and method for providing both freshness and performance benefits, such as scent intensity and longevity and hard surface shine, of a cleaning composition on a hard surface using perfume raw materials (PRMs) in an aqueous carrier.

BACKGROUND

Hard surface cleaning compositions are used for cleaning and treating hard surfaces.
Preferably, the hard surface cleaning composition is formulated to be an “all purpose” hard surface cleaning composition. That is, the hard surface cleaning composition is formulated to be suitable for cleaning a variety of surfaces. However, it historically has been challenging to formulate a hard surface cleaning composition which effectively cleans tiles, and more delicate surfaces such as wood, stainless steel, linoleum, marble, and the like while delivering freshness benefits in a phase stable formulation without compromising cleaning. Typically, freshness benefits in aqueous cleaning compositions are achieved by the emulsification of highly hydrophobic perfumes with high level of surfactants which then negatively affect cleaning and shine benefits of the treated surface. For example, although surfactants are used, the concentrations need to be minimized otherwise the surfactants may leave residue and result in low shine, and an impression that the surface is not yet sufficiently clean. Solvent levels are also best minimized to avoid environmental considerations or negatively impact on scent. Additionally, many solvents used are high Volatile Organic Compounds (VOC). VOC materials pose challenges for negatively impacting perfume compositions by affecting their scent perception, also known as perfume's character, as well as concerns around flashpoint regulations. Given these challenges, formulators typically avoid elevated levels of solvents and surfactants, which in turn minimizes the use or concentration of relatively more hydrophobic PRMs. This reduces the breadth of available PRMs and thus scent experiences to users. These challenges are exacerbated when formulations contain especially high levels of water and/or high levels of PRMs.
Therefore, there is a need for a cleaning composition that provides high shine with a wide variety of scent experiences enabled by more hydrophobic PRMs while minimizing levels of solvents and surfactants.

SUMMARY

Aspects of the present disclosure include a hard surface cleaning composition comprising: at least 85% by weight of water, at least 0.0015% of by weight of alkoxylated phenol; and a perfume, wherein the perfume comprises at least 60% by weight of the Perfume Raw Materials having C log P greater than 1.0. The composition has a Shine Result of between 0.1 and 2.0 and an NTU of between 1 and 200.
Aspects of the present disclosure also include methods of improving shine of a hard surface, including the steps of wetting the hard surface with the hard surface cleaning composition and removing the cleaning composition from the hard surface with a disposable dry cleaning wipe.
Yet another aspect of of the present disclosure also include a disposable premoistened pad for cleaning hard surfaces including a substrate and the liquid hard surface cleaning composition. The substrate is impregnated with the cleaning composition
Aspects of the present disclosure also include a cleaning implement including a handle; a plastic head; a cleaning pad removably connectable with the plastic head; a reservoir connected with or separated from the handle; and the cleaning composition disposed in the reservoir.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1A is a top perspective view an exemplary cleaning pad according to the present invention shown partially in cutaway.

FIG. 1B is a bottom plan view of the cleaning pad of FIG. 1A, shown partially in cutaway and having one attachment strip truncated for clarity.

FIG. 2 is a schematic, vertical sectional view taken along lines 2-2 of FIG. 1B.

FIG. 3 is a perspective view of a cleaning implement usable with the cleaning pad of the present invention and showing the cleaning pad in position to be removably attached to the cleaning implement.

FIG. 4 Illustrates the benefit on intensity profile and longevity of the cleaning composition with high perfume concentration emulsified with alkoxylated phenol (Inventive Sample) vs a non-emulsified low perfume concentration (Comparative Sample) as perceived by a sensory panel using Perfume Composition I.

FIG. 5 Illustrates the benefit on longevity vs perfume concentration, indicating the benefits in odor detection threshold (ODT) and longevity for higher perfume concentrations.

DETAILED DESCRIPTION

Perfume raw materials (PRMs) are typically formulated with water to make cleaning compositions. However, because of the hydrophobic nature of PRMs, solvents and/or surfactants are used to solubilize and emulsify the PRMs in formulations with high water content. Solvents suitable for solubilizing PRMs typically include alcohols, polyols and mixtures thereof.
The present invention is based on the surprising discovery that the cleaning composition of the present invention comprising high levels of water, perfume and relatively low levels of alkoxylated phenol can improve solubility of a perfume PRMs having a C log P greater than 1.0 in water content thereby providing phase stable cleaning compositions with higher perfume intensity and longevity.
The alkoxylated phenol may be an ethoxylated phenol. Having the combination of PRMs and alkoxylated phenol enables a phase stable cleaning composition and a wider range of PRMs may be formulated.
In the following description, the composition described is a floor cleaning composition. However, it is contemplated that the composition may be configured for use in a variety of applications to provide cleaning and freshness on hard surfaces or other inanimate surfaces.
Prior to describing the present invention in detail, the following terms are defined for clarity. Terms not defined should be given their ordinary meaning as understood by a skilled person in the relevant art.
The term “inanimate surface” as used herein refers to surfaces including but not limited to household surfaces such as countertops, floors, garbage cans, ceilings, walls, carpet padding, air filters, and the like.
The term “C log P” as used herein refers to a calculated log P (“C log P”) value of a volatile material such as for example a perfume raw material. An octanol/water partition coefficient of a volatile material is the ratio between its equilibrium concentrations in octanol and in water. The partition coefficients of the perfume material used in a cleaning composition may more conveniently be given in the form of its logarithm to the base 10, log P. The C log P is determined by the fragment approach of Hansch and Leo (cf, A. Leo, in Comprehensive Medicinal Chemistry, vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990).
The term “odor detection threshold” as used herein refers to the lowest concentration of a perfume composition that is perceivable by the human sense of smell and it is correlated to longevity of the perfume composition.
The term “essentially free of” a component means that no amount of that component is deliberately incorporated into the respective premix, or composition. Preferably, “essentially free of” a component means that no amount of that component is present in the respective premix, or composition, but may be present as trace impurities.
As used herein, “isotropic” means a clear mixture, having little or no visible haziness, phase separation and/or dispersed particles, and having a uniform transparent appearance.
As defined herein, “stable” means that no visible phase separation is observed for a premix kept at 25° C. for a period of at least two weeks, or at least four weeks, or greater than a month or greater than four months, as measured using the Floc Formation Test, described in USPA 2008/0263780 A1.
By “Low volatile organic compound hard surface cleaning composition”, it is meant herein a finished product having low volatile organic compound (“VOC”) content like, for example, a maximum of 0.5% by weight of the composition of VOCs, however, it is noted that fragrance is exempted from this value up to 2% by the weight of the finished product.
All percentages, ratios and proportions used herein are by weight percent of the premix, unless otherwise specified. All average values are calculated “by weight” of the premix, unless otherwise expressly indicated.
All measurements are performed at 25° C. unless otherwise specified.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
I. Liquid Hard Surface Cleaning Composition
By “liquid hard surface cleaning composition,” it is meant herein a liquid composition for cleaning and hard surfaces found in households, especially domestic households. Surfaces to be cleaned include kitchens and bathrooms, e.g., floors, walls, tiles, windows, cupboards, sinks, showers, shower plasticised curtains, wash basins, WCs, fixtures and fittings and the like made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, steel, kitchen work surfaces, any plastics, wood, plasticised wood, metal or any painted or varnished or sealed surface and the like. Household hard surfaces also include household appliances including, but not limited to refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on. Such hard surfaces may be found both in private households as well as in commercial, institutional and industrial environments.
A. Water
A liquid hard surface cleaning composition of the present invention may comprise at least 85%, by weight of the composition of water. The water may be in an amount from 85% to 99.5%, from 90% to 99.5%, from 95% to 99.5%, 95%, or different combinations of the upper and lower percentages described above or combinations of any integer in the ranges listed above, of water by weight of the composition. The water may be distilled, deionized or tap water. Having high levels of water enable the cleaning composition to wet and spread through cleaning surface for the purpose of cleaning while reducing the amount of residue left behind, resulting in improved shine.
B. Alkoxylated Phenol
The hard surface cleaning composition has alkoxylated phenol in a level of at least 0.0015% by weight of the composition. Alkoxylation is a chemical reaction that involves the addition of an epoxide which is an alkoxylating agent to another compound. Epoxides may be lower molecular weight epoxides (oxiranes) such as ethylene oxide, propylene oxide and butylene oxide. These epoxides are capable of reacting with hydroxyl generally under base catalysis, causing a ring opening and the addition of an oxyalkylene group. The resulting compound contains a hydroxyl group, so a varied number of moles of oxide can be added. Alkoxylation of a phenol-containing compound relates to reaction of mixtures of oxides with the phenol containing compound which produces hydroxy alkyl phenyl ether compounds (also known as alkoxylated phenols). A process for alkoxylation of phenols is described in U.S. Pat. No. 4,261,922. A phenol-containing compound has the following structure and the molecular formulae is C₆H₅OH.
The alkoxylated phenol may be selected from the group consisting of: propoxylated phenol, ethoxylated phenol, and combinations thereof, preferably ethoxylated phenol.
Accordingly, the reaction of ethylene oxide with a phenol containing compound results in ethoxylated phenol as shown in the following reaction:
ROH+C₂H₄O→ROCH₂CH₂OH,
wherein ROH is phenol containing compound.
Similarly, the reaction of propylene oxide with a phenol containing compound results in propoxylated phenol as shown in the following reaction:
ROH+nOCH₂CHCH₃→R(OCH₂CHCH₃)_nOH,
wherein ROH is phenol containing compound. Ethoxylation and propoxylation of phenol containing compounds may be performed according to known processes.
In the following description, the alkoxylated phenol described is an ethoxylated phenol. However, it is contemplated that other alkoxylated phenols, such as propoxylated, butoxylated, or mixtures thereof, may be configured for solubilizing the PRMs described hereinafter as long as the alkoxylated phenol is soluble in water and solubilizes the PRMs in water.
The ethoxylated phenol may be in an amount of at least 0.0015%, preferably from 0.0015% to 9%, 0.0015% to 3.5%, more preferably, 0.0015% to 2%, even more preferably 0.0015% to 1.5%, by weight of the cleaning composition.
The ethoxylated phenol may have a structure according to Formula I:

- wherein n is selected from 0 to 20, preferably from 5 to 15, more preferably from 5 to 10, even more preferably from 5 to 7; preferably n is an average value of from 5 to 15, preferably from 5 to 10, more preferably from 5 to 7.

Referring to Formula I, “n” is a numerical value corresponding to a number of ethoxylates in the ethoxylated phenol and defines the ethoxylate chain of the ethoxylated phenol. Without wishing to be bound by theory, the ethoxylated phenol for the cleaning composition according to the present invention may have different ethoxylates have ethoxylate chains of differing lengths to meet different cleaning product specifications in order to be both water-soluble and oil-soluble in a cleaning composition which has a high level of water and a perfume composition having at least 60% of PRMs having a C log P>1.
Ethoxylated phenols commercially available from Dow under the commercial names of Dowanol™ Glycol Ethers are set out in Table 1 below. As shown in the data described hereinafter in the Examples, use of ethoxylated phenols in which n is an average value from 5 to 15 results in a clear composition (see Example 6) relative to comparative ethoxylated phenols in which n is an average value from 1 to 2.

TABLE 2

	Commercial Name

DOWANOL		DOWANOL
EPh Glycol	DOWANOL	EPh6
Ether	DiEPh	Glycol Ether

Chemical Nomenclature

		Diethylene
	Ethylene	glycol	Polyethylene
	glycol	phenyl	glycol
	phenyl ether	ether	phenyl ether

Physical Property (Units)
Molecular Weight (g/mol)	138.2	182.2	358/4
Boiling point (° C. @	244	282	>350
760 mmHg)
Flash Point (° C.)	121	138	>149
Evaporation Rate	0.001	0.0002	<0.0001
(nBuAc = 1)
Specific Gravity	1.109	1.112	1.12
at 25/25° C.
Density (g/cc at 25° C.)	1.106	1.109	1.120
Viscosity (cP at 25° C.)	21.5	30	89-93
Vapor Pressure	0.004	<0.002	<0.0001
(mm Hg at 20° C.)
Surface Tension	42.0	37.7	45.2
(dynes/cm)
Hansens Solubility
Parameters (joules/cm³)^1/2
delta d	17.8	16.4	17.4
delta p	5.7	6.7	6.6
delta h	14.3	11.6	10.6
Solubility	2.5	4.00	Infinity
(wt % at 25° C. In Water)
Solubility	9.0	22	Infinity
(wt % at 25° C. Water In)

The compositions of the present disclosure preferably have a viscosity from 1 cps to 650 cps, more preferably of from 100 cps to 550 cps, more preferably from 150 cps to 450 cps, most preferably from 250 cps to 350 cps when measured at 20° C. with a AD1000 Advanced Rheometer from Atlas® shear rate 10 s−1 with a coned spindle of 40 mm with a cone angle 2° and a truncation of ±60 μm.
The pH is preferably from 3.0 to 12, more preferably from 5 to 8 and most preferably from 6 to 7.
It will be understood that the compositions herein may further comprise an acid or base to adjust pH as appropriate.
A suitable acid for use herein is an organic and/or an inorganic acid. A preferred organic acid for use herein has a pKa of less than 7. A suitable organic acid is selected from the group consisting of: citric acid, lactic acid, glycolic acid, maleic acid, malic acid, succinic acid, glutaric acid and adipic acid and mixtures thereof. A suitable inorganic acid can be selected from the group consisting of: hydrochloric acid, sulphuric acid, phosphoric acid and mixtures thereof.
A typical level of such acids, when present, is from 0.001% to 1.0% by weight of the total composition, preferably from 0.005% to 0.5% and more preferably from 0.01% to 0.05%.
A suitable base to be used herein is an organic and/or inorganic base. Suitable bases for use herein are the caustic alkalis, such as sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such, as sodium and/or potassium oxide or mixtures thereof. A preferred base is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide.
Other suitable bases include ammonia, ammonium carbonate, K₂CO₃, Na₂CO₃and alkanolamines (such as monoethanolamine, triethanolamine, aminomethylpropanol, and mixtures thereof).
Typical levels of such bases, when present, are from 0.001% to 1.0% by weight of the total composition, preferably from 0.005% to 0.5% and more preferably from 0.01% to 0.05%.
C. Solvent
The liquid hard surface cleaning compositions preferably comprises a solvent. Suitable solvents may be selected from the group consisting of: ethers and diethers having from 4 to 14 carbon atoms; glycols or alkoxylated glycols; alkoxylated aromatic alcohols; aromatic alcohols; alkoxylated aliphatic alcohols; aliphatic alcohols; C₈-C₁₄alkyl and cycloalkyl hydrocarbons and halohydrocarbons; C₆-C₁₆glycol ethers; terpenes; and mixtures thereof.
In the present invention, solvents can be selected for its level of water solubility or its Hydrophilic-Lipophilic Balance or HLB value. The lower the HLB value the less water soluble the solvent and the more oil soluble or oil compatible. For example, an HLB value of 0 corresponds to a completely lipophilic/hydrophobic molecule or oil soluble molecule, and an HLB value of 20 corresponds to a completely hydrophilic/lipophobic or water-soluble molecule.
The liquid hard surface cleaning compositions preferably comprises a glycol ether solvent. The solvent comprises a glycol ether solvent with an HLB value of 5.5 to 7.0.
A glycol ether having an HLB between 5.5 and 7.0 may be selected from the group consisting of: Tripropylene glycol methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, diethylene glycol monohexyl ether or butyl carbitol, ethylene glycol monohexyl ether or hexyl CELLOSOLVE™, ethylene glycol phenyl ether or phenoxyethanol, propylene glycol phenyl ether or dipropylene glycol phenyl ether solvent and combinations thereof. Exemplary glycol ethers having an HLB between 5.5 and 7.0 are DOWANOL™ TPM, DOWANOL™ PnB and DOWANOL™ DPnB, Hexyl CARBITOL™ Solvent, Hexyl CELLOSOLVE™ Solvent, DOWANOL™ EPH, DOWANOL™ PPh or DOWANOL™ DiPPh Glycol from the Dow Chemical Company.
The phenyl glycol ether solvent having an HLB between 5.5 and 7.0 may be present at a level of 0.05 wt. % to 3.50 wt. %, more preferably 0.1 wt. % to 1.5 wt. %, most preferably 0.3 wt. % to 0.9 wt. %, by weight of the overall composition.
D. Castor Oil Surfactants
The liquid hard surface cleaning compositions preferably comprises a polyoxyethylene castor oil ethers or polyoxyethylene hardened castor oil ethers or mixtures thereof, which are either partially or fully hydrogenated. These ethoxylates have the following general formulae:
These ethoxylates can be used alone or in any mixture thereof. The average ethylene oxide addition mole number (i.e., l+m+n+x+y+z in the above formula) of these ethoxylates is generally from about 7 to about 100, and preferably from about 20 to about 80. Castor oil surfactants are commercially available from Nikko under the trade names HCO 40 and HCO 60 and from BASF under the trade names Cremphor™ RH 40, RH 60, and CO 60.
E. Amphoteric Surfactants
The liquid hard surface cleaning composition of the present disclosure may include an amine oxide surfactant. The amine oxide may be present at a level of 0.005 wt. % to 0.5 wt. %, more preferably 0.01 wt. % to 0.1 wt. %, most preferably 0.04 wt. % to 0.06 wt. %, by weight of the overall composition.
Suitable amphoteric surfactants include amine oxide surfactants which include: R₁R₂R₃NO wherein each of R₁, R₂and R₃is independently a saturated or unsaturated, substituted or unsubstituted, linear or branched hydrocarbon chain having from 10 to 30 carbon atoms. Preferred amine oxide surfactants are amine oxides having the following formula: R₁R₂R₃NO wherein R₁is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16 and wherein R₂and R₃are independently saturated or unsaturated, substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups. R₁may be a saturated or unsaturated, substituted or unsubstituted linear or branched hydrocarbon chain.
A highly preferred amine oxide is C₁₂-C₁₄dimethyl amine oxide, commercially available from Albright & Wilson, C₁₂-C₁₄amine oxides commercially available under the trade name Genaminox® LA from Clariant or AROMOX® DMC from AKZO Nobel.
Other suitable amphoteric surfactants include dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate, as taught in U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those taught in U.S. Pat. No. 2,438,091, and the products sold under the trade name “Miranol”, as described in U.S. Pat. No. 2,528,378. Other suitable additional surfactants can be found in McCutcheon's Detergents and Emulsifers, North American Ed. 1980.
F. Non-Ionic Surfactants
Suitable non-ionic surfactants are ethoxylated alkoxylated nonionic surfactant. Preferably, the liquid hard surface cleaning composition comprises the ethoxylated alkoxylated nonionic surfactant at a level of from 0.0001 to 1% wt %, more preferably from 0.001 to 0.5 wt %, most preferably from 0.001 to 0.04 wt % of the composition. The ethoxylated alkoxylated nonionic surfactant is preferably selected from the group consisting of: esterified alkyl alkoxylated surfactant; alkyl ethoxy alkoxy alcohol, wherein the alkoxy part of the molecule is preferably propoxy, or butoxy, or propoxy-butoxy; polyoxyalkylene block copolymers, and mixtures thereof.
The preferred ethoxylated alkoxylated nonionic surfactant is an esterified alkyl alkoxylated surfactant of general formula (I):
where
R is a branched or unbranched alkyl radical having 8 to 16 carbon atoms, preferably from 10 to 16 and more preferably from 12 to 15;
R³, R¹independently of one another, are hydrogen or a branched or unbranched alkyl radical having 1 to 5 carbon atoms; preferably R³and R¹are hydrogen
R²is an unbranched alkyl radical having 5 to 17 carbon atoms; preferably from 6 to 14 carbon atoms
l, n independently of one another, are a number from 1 to 5 and
m is a number from 8 to 50; and
Preferably, the weight average molecular weight of the ethoxylated alkoxylated nonionic surfactant of formula (I) is from 950 to 2300 g/mol, more preferably from 1200 to 1900 g/mol.
R is preferably from 12 to 15, preferably 13 carbon atoms. R³and R¹are preferably hydrogen. Component l is preferably 5. n is preferably 1. m is preferably from 13 to 35, more preferably 15 to 25, most preferably 22. R²is preferably from 6 to 14 carbon atoms.
The hard surface cleaning composition of the invention provides especially high shine when the esterified alkyl alkoxylated surfactant is as follows: R has from 12 to 15, preferably 13 carbon atoms, R³is hydrogen, R¹is hydrogen, component l is 5, n is 1, m is from 15 to 25, preferably 22 and R²has from 6 to 14 carbon atoms and the alcohol ethoxylated has an aliphatic alcohol chain containing from 10 to 14, more preferably 13 carbon atoms and from 5 to 8, more preferably 7 molecules of ethylene oxide.
Preferably, the ethoxylated alkoxylated nonionic surfactant can be a polyoxyalkylene copolymer. The polyoxyalkylene copolymer can be a block-heteric ethoxylated alkoxylated nonionic surfactant, though block-block surfactants are preferred. Suitable polyoxyalkylene block copolymers include ethylene oxide/propylene oxide block polymers, of formula (II):
(EO)_x(PO)_y(EO)_x, or (II)
(PO)_x(EO)_y(PO)_x (II)
wherein EO represents an ethylene oxide unit, PO represents a propylene oxide unit, and x and y are numbers detailing the average number of moles ethylene oxide and propylene oxide in each mole of product. Such materials tend to have higher molecular weights than most non-ionic surfactants, and as such can range between 1000 and 30000 g/mol, although the molecular weight should be above 2200 and preferably below 13000. A preferred range for the molecular weight of the polymeric non-ionic surfactant is from 2400 to 11500 Daltons. BASF (Mount Olive, N.J.) manufactures a suitable set of derivatives and markets them under the Pluronic trademarks. Examples of these are Pluronic (trademark) F77, L62 and F88 which have the molecular weight of 6600, 2450 and 11400 g/mol respectively. An especially preferred example of a useful polymeric non-ionic surfactant is Pluronic (trademark) F77.
Other suitable ethoxylated alkoxylated nonionic surfactants are described in Chapter 7 of Surfactant Science and Technology, Third Edition, Wiley Press, ISBN 978-0-471-68024-6.
The ethoxylated alkoxylated nonionic surfactant preferably provides a wetting effect of from 15 to 350 s, more preferably from 60 to 200 s, even more preferably from 75 to 150 s. The wetting effect is measured according to EN 1772, using 1 g/l of the ethoxylated alkoxylated nonionic surfactant in distilled water, at 23° C., with 2 g soda/l.
The ethoxylated alkoxylated nonionic surfactants preferably are low foaming non-ionic surfactants that are alkoxylated and include unbranched fatty alcohols that may contain high amounts of alkene oxide and ethylene oxide. For example, preferred ethoxylated alkoxylated nonionic surfactants may include those sold by BASF under the “Plurafac” trademark, especially Plurafac LF 131 (wetting effect of 25 s), LF 132 (wetting effect of 70 s), LF 231 (wetting effect of 40 s), LF 431 (wetting effect of 30 s), LF 1530 (wetting effect >300 s), LF 731 (wetting effect of 100 s), LF 1430 (wetting effect >300 s) and LF 7319 (wetting effect of 100 s).
The ethoxylated alkoxylated nonionic surfactants preferably are not hydrogenated and, therefore, the fatty alcohol chains do not terminate in a hydrogen group. Examples of such hydrogenated non-ionic surfactants include Plurafac 305 and Plurafac 204.
Suitable alkoxylated nonionic surfactants also include primary C₆-C₁₆alcohol polyglycol ether i.e. ethoxylated alcohols having 6 to 16 carbon atoms in the alkyl moiety and 4 to 30 ethylene oxide (EO) units. When referred to for example C_9-14it is meant average carbons and alternative reference to for example EO8 is meant average ethylene oxide units.
Suitable alkoxylated nonionic surfactants are according to the formula RO-(A)_nH, wherein: R is a C₆to C₁₈, preferably a C₈to C₁₆, more preferably a C₈to C₁₂alkyl chain, or a C₆to C₂₈alkyl benzene chain; A is an ethoxy or propoxy or butoxy unit, and wherein n is from 1 to 30, preferably from 1 to 15 and, more preferably from 4 to 12 even more preferably from 5 to 10. Preferred R chains for use herein are the C₈to C₂₂alkyl chains. Even more preferred R chains for use herein are the C₉to C₁₂alkyl chains. R can be linear or branched alkyl chain.
Suitable ethoxylated nonionic surfactants for use herein are Dobanol® 91-2.5 (HLB=8.1; R is a mixture of C₉and C₁₁alkyl chains, n is 2.5), Dobanol® 91-10 (HLB=14.2; R is a mixture of C₉to C₁₁alkyl chains, n is 10), Dobanol® 91-12 (HLB=14.5; R is a mixture of C₉to C₁₁alkyl chains, n is 12), Greenbentine DE80 (HLB=13.8, 98 wt % C10 linear alkyl chain, n is 8), Marlipal 10-8 (HLB=13.8, R is a C10 linear alkyl chain, n is 8), Lialethl® 11-5 (R is a C₁₁alkyl chain, n is 5), Isalchem® 1-5 (R is a mixture of linear and branched C11 alkyl chain, n is 5), Lialethl®11-21 (R is a mixture of linear and branched C11 alkyl chain, n is 21), Isalchem® 11-21 (R is a C₁₁branched alkyl chain, n is 21), Empilan® KBE21 (R is a mixture of C₁₂and C₁₄alkyl chains, n is 21) or mixtures thereof. Preferred herein are Dobanol® 91-5, Neodol® 11-5, Lialethl® 11-21 Lialethl® 11-5 Isalchem® 11-5 Isalchem® 11-21 Dobanol® 91-8, or Dobanol® 91-10, or Dobanol® 91-12, or mixtures thereof. These Dobanol®/Neodol® surfactants are commercially available from SHELL. These Lutensol® surfactants are commercially available from BASF and these Tergitol® surfactants are commercially available from Dow Chemicals.
Suitable chemical processes for preparing the alkoxylated nonionic surfactants for use herein include condensation of corresponding alcohols with alkylene oxide, in the desired proportions. Such processes are well known to the person skilled in the art and have been extensively described in the art, including the OXO process and various derivatives thereof. Suitable alkoxylated fatty alcohol nonionic surfactants, produced using the OXO process, have been marketed under the tradename NEODOL® by the Shell Chemical Company. Alternatively, suitable alkoxylated nonionic surfactants can be prepared by other processes such as the Ziegler process, in addition to derivatives of the OXO or Ziegler processes.
Preferably, said alkoxylated nonionic surfactant is a C_9-11EO5 alkylethoxylate, C_12-14EO5 alkylethoxylate, a C₁₁EO5 alkylethoxylate, C_12-14EO21 alkylethoxylate, or a C_9-11EO8 alkylethoxylate or a mixture thereof. Most preferably, said alkoxylated nonionic surfactant is a C₁₁EO5 alkylethoxylate or a C_9-11EO8 alkylethoxylate or a mixture thereof.
Another suitable class of non-ionic surfactants are Alkyl polyglycosides, which are biodegradable non-ionic surfactants which are well known in the art. Suitable alkyl polyglycosides can have the general formula C_nH_2n+1O(C₆H₁₀O₅)_xH wherein n is preferably from 9 to 16, more preferably 11 to 14, and x is preferably from 1 to 2, more preferably 1.3 to 1.6. Such alkyl polyglycosides provide a good balance between anti-foam activity and detergency. Alkyl polyglycoside surfactants are commercially available in a large variety. An example of a very suitable alkyl poly glycoside product is Planteren APG 600, which is essentially an aqueous dispersion of alkyl polyglycosides wherein n is about 13 and x is about 1.4.
The additional nonionic surfactant is preferably a low molecular weight nonionic surfactant, having a molecular weight of less than 950 g/mol, more preferably less than 500 g/mol.
Another suitable non-ionic surfactants are zwitterionic surfactants. Zwitterionic surfactants typically contain both cationic and anionic groups in substantially equivalent proportions so as to be electrically neutral at the pH of use. The typical cationic group is a quaternary ammonium group, other positively charged groups like phosphonium, imidazolium and sulfonium groups can be used. The typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
Some common examples of zwitterionic surfactants (such as betaine/sulphobetaine surfacants) are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082. For example Coconut dimethyl betaine is commercially available from Seppic under the trade name of Amonyl 265®. Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB/L®. A further example of betaine is Lauryl-imminodipropionate commercially available from Rhodia under the trade name Mirataine H2C-HA®.
Sulfobetaine surfactants are particularly preferred, since they can improve soap scum cleaning. Examples of suitable sulfobetaine surfactants include tallow bis(hydroxyethyl) sulphobetaine, cocoamido propyl hydroxy sulphobetaines which are commercially available from Rhodia and Witco, under the trade name of Mirataine CBS® and ReWoteric AM CAS 15® respectively.
G. Anionic Surfactant
The liquid hard surface cleaning composition may comprise an anionic surfactant. In one particularly preferred embodiment, the composition is essentially free of an anionic surfactant. If included, however, the anionic surfactant may be selected from the group consisting of: an alkyl sulphate, an alkyl alkoxylated sulphate, a sulphonic acid or sulphonate surfactant, and mixtures thereof.
H. Copolymer:
The cleaning composition may comprise from 0.005% to 1.5%, more preferably from 0.01% to 1%, yet more preferably from 0.01% to 5%, most preferably from 0.01 to 0.06% by weight of the cleaning composition, of a copolymer that comprises monomers selected from the group comprising monomers of formula (III) (Monomer A) and monomers of formula (IVa-IVd) (Monomer B) (hereinafter referred to as “the copolymer”). The copolymer comprises from 60 to 99%, preferably from 70 to 95% and especially from 80 to 90% by weight of at least one monoethylenically unsaturated polyalkylene oxide monomer of the formula (III) (monomer A)
wherein Y of formula (III) is selected from —O— and —NH—; if Y of formula (III) is —O—, X of formula (III) is selected from —CH₂— or —CO—, if Y of formula (III) is —NH—, X of formula (III) is —CO—; R¹of formula (III) is selected from hydrogen, methyl, and mixtures thereof; R²of formula (III) is independently selected from linear or branched C₂-C₆-alkylene radicals, which may be arranged blockwise or randomly; R³of formula (III) is selected from hydrogen, C₁-C₄-alkyl, and mixtures thereof; n of formula (III) is an integer from 5 to 100, preferably from 10 to 70 and more preferably from 20 to 50.
The copolymer comprises from 1 to 40%, preferably from 2 to 30% and especially from 5 to 20% by weight of at least one quaternized nitrogen-containing monoethylenically unsaturated monomer of formula (IVa-IVd) (monomer B).
The monomers are selected such that the copolymer has a weight average molecular weight (M_w) of from 5,000 to 500,000 g/mol, preferably from greater than 7,000 to 150,000 g/mol and especially from 10,000 to 80,000 g/mol.
The copolymer preferably has a net positive charge at a pH of 5. The copolymer for use in the present disclosure may further comprise monomers C and/or D. Monomer C may comprise from 0% to 15%, preferably from 0 to 10% and especially from 1 to 7% by weight of the copolymer of an anionic monoethylenically unsaturated monomer.
Monomer D may comprise from 0% to 40%, preferably from 1 to 30% and especially from 5 to 20% by weight of the copolymer of other non-ionic monoethylenically unsaturated monomers.
Preferred copolymers according to the present disclosure comprise, as copolymerized Monomer A, monoethylenically unsaturated polyalkylene oxide monomers of formula (III) in which Y of formula (III) is —O—; X of formula (III) is —CO—; R¹of formula (III) is hydrogen or methyl; R²of formula (III) is independently selected from linear or branched C₂-C₄-alkylene radicals arranged blockwise or randomly, preferably ethylene, 1,2- or 1,3-propylene or mixtures thereof, particularly preferably ethylene; R³of formula (III) is methyl; and n is an integer from 20 to 50.
Monomer A
A monomer A for use in the copolymer of the present disclosure may be, for example:

- (a) reaction products of (meth)acrylic acid with polyalkylene glycols which are not terminally capped, terminally capped at one end by alkyl radicals; and
- (b) alkenyl ethers of polyalkylene glycols which are not terminally capped or terminally capped at one end by alkyl radicals.

Preferred monomer A is the (meth)acrylates and the allyl ethers, where the acrylates and primarily the methacrylates are particularly preferred. Particularly suitable examples of the monomer A are:

- (a) methylpolyethylene glycol (meth)acrylate and (meth)acrylamide, methylpolypropylene glycol (meth)acrylate and (meth)acrylamide, methylpolybutylene glycol (meth)acrylate and (meth)acrylamide, methylpoly(propylene oxide-co-ethylene oxide) (meth)acrylate and (meth)acrylamide, ethylpolyethylene glycol (meth)acrylate and (meth)acrylamide, ethylpolypropylene glycol (meth)acrylate and (meth)acrylamide, ethylpolybutylene glycol (meth)acrylate and (meth)acrylamide and ethylpoly(propylene oxide-co-ethylene oxide) (meth)acrylate and (meth)acrylamide, each with 5 to 100, preferably 10 to 70 and particularly preferably 20 to 50, alkylene oxide units, where methylpolyethylene glycol acrylate is preferred and methylpolyethylene glycol methacrylate is particularly preferred;
- (b) ethylene glycol allyl ethers and methylethylene glycol allyl ethers, propylene glycol allyl ethers and methylpropylene glycol allyl ethers each with 5 to 100, preferably 10 to 70 and particularly preferably 20 to 50, alkylene oxide units.

The proportion of Monomer A in the copolymer according to the present disclosure is 60% to 99% by weight, preferably 70% to 95%, more preferably from 80% to 90% by weight of the copolymer.
Monomer B
A monomer B that is particularly suitable for the copolymer of the present disclosure includes the quaternization products of 1-vinylimidazoles, of vinylpyridines, of (meth)acrylic esters with amino alcohols, in particular N,N-di-C₁-C₄-alkylamino-C₂-C₆-alcohols, of amino-containing (meth)acrylamides, in particular N,N-di-C₁-C₄-alkyl-amino-C₂-C₆-alkylamides of (meth)acrylic acid, and of diallylalkylamines, in particular diallyl-C₁-C₄-alkylamines.
Suitable monomers B have the formula IVa to IVd:
wherein R of formula IVa to IVd is selected from C₁-C₄-alkyl or benzyl, preferably methyl, ethyl or benzyl; R¹of formula IVc is selected from hydrogen or methyl; Y of formula IVc is selected from —O— or —NH—; A of formula IVc is selected from C₁-C₆-alkylene, preferably straight-chain or branched C₂-C₄-alkylene, in particular 1,2-ethylene, 1,3- and 1,2-propylene or 1,4-butylene; X— of formula IVa to IVd is selected from halide, such as iodide and preferably chloride or bromide, C₁-C₄-alkyl sulfate, preferably methyl sulfate or ethyl sulfate, C₁-C₄-alkylsulfonate, preferably methylsulfonate or ethylsulfonate, C₁-C₄-alkyl carbonate; and mixtures thereof.
Specific examples of preferred monomer B that may be utilized in the present disclosure are:

- (a) 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, 3-ethyl-1-vinylimidazolium ethyl sulfate, 3-ethyl-1-vinylimidazolium chloride and 3-benzyl-1-vinylimidazolium chloride;
- (b) 1-methyl-4-vinylpyridinium chloride, 1-methyl-4-vinylpyridinium methyl sulfate and 1-benzyl-4-vinylpyridinium chloride;
- (c) 3-methacrylamido-N,N,N-trimethylpropan-1-aminium chloride, 3-acryl-N,N,N-trimethylpropan-1-aminium chloride, 3-acryl-N,N,N-trimethylpropan-1-aminium methylsulfate, 3-methacryl-N,N,N-trimethylpropan-1-aminium chloride, 3-methacryl-N,N,N-trimethylpropan-1-aminium methylsulfate, 2-acrylamido-N,N,N-trimethylethan-1-aminium chloride, 2-acryl-N,N,N-trimethylethan-1-aminium chloride, 2-acryl-N,N,N-trimethylethan-1-aminium methyl sulfate, 2-methacryl-N,N,N-trimethylethan-1-aminium chloride, 2-methacryl-N,N,N-trimethylethan-1-aminium methyl sulfate, 2-acryl-N,N-dimethyl-N-ethylethan-1-aminium ethylsulfate, 2-methacryl-N,N-dimethyl-N-ethylethan-1-aminium ethylsulfate, and
- (d) dimethyldiallylammonium chloride and diethyldiallylammonium chloride.

A preferred monomer B is selected from 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, 3-methacryl-N,N,N-trimethylpropan-1-aminium chloride, 2-methacryl-N,N,N-trimethylethan-1-aminium chloride, 2-methacryl-N,N-dimethyl-N-ethylethan-1-aminium ethylsulfate, and dimethyldiallylammonium chloride.
The copolymer according to the present disclosure comprises I % to 40% by weight, preferably 2% to 30%, and especially preferable from 5 to 20% by weight of the copolymer, of Monomer B. The weight ratio of Monomer A to Monomer B is preferably equal to or greater than 2:1, preferably 3:1 to 5:1.
Monomer C
As optional components of the copolymer of the present disclosure, monomers C and D may also be utilized. Monomer C is selected from anionic monoethylenically unsaturated monomers.
Suitable monomer C may be selected from:

- (a) α,β-unsaturated monocarboxylic acids which preferably have 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, 2-methylenebutanoic acid, crotonic acid and vinylacetic acid, preference being given to acrylic acid and methacrylic acid;
- (b) unsaturated dicarboxylic acids, which preferably have 4 to 6 carbon atoms, such as itaconic acid and maleic acid, anhydrides thereof, such as maleic anhydride;
- (c) ethylenically unsaturated sulfonic acids, such as vinylsulfonic acid, acrylamido-propanesulfonic acid, methallylsulfonic acid, methacrylsulfonic acid, m- and p-styrenesulfonic acid, (meth)acrylamidomethanesulfonic acid, (meth)acrylamidoethanesulfonic acid, (meth)acrylamidopropanesulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonicacid, 2-acrylamido-2-butanesulfonicacid, 3-methacrylamido-2-hydroxypropanesulfonic acid, methanesulfonic acid acrylate, ethanesulfonic acid acrylate, propanesulfonic acid acrylate, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid and 1-allyloxy-2-hydroxypropanesulfonic acid; and
- (d) ethylenically unsaturated phosphonic acids, such as vinylphosphonic acid and m- and p-styrenephosphonic acid.

The anionic Monomer C can be present in the form of water soluble free acids or in water-soluble salt form, especially in the form of alkali metal and ammonium, in particular alkylammonium, salts, and preferred salts being the sodium salts.
A preferred Monomer C may be selected from acrylic acid, methacrylic acid, maleic acid, vinylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid and vinylphosphonic acid, particular preference being given to acrylic acid, methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid.
The proportion of monomer C in the copolymer of the present disclosure can be up to 15% by weight, preferably from 1% to 5% by weight of the copolymer.
If monomer C is present in the copolymer of the present disclosure, then, the molar ratio of monomer B to monomer C is greater than 1. The weight ratio of Monomer A to monomer C is preferably equal to or greater than 4:1, more preferably equal to or greater than 5:1. Additionally, the weight ratio of monomer B to monomer C is equal or greater than 2:1, and even more preferable from 2.5:1
Monomer D
As an optional component of the copolymer of the present disclosure, monomer D may also be utilized. Monomer D is selected from nonionic monoethylenically unsaturated monomers selected from:

- (a) esters of monoethylenically unsaturated C₃-C₆-carboxylic acids, especially acrylic acid and methacrylic acid, with monohydric C₁-C₂₂-alcohols, in particular C₁-C₁₆-alcohols; and hydroxyalkyl esters of monoethylenically unsaturated C₃-C₆-carboyxlic acids, especially acrylic acid and methacrylic acid, with divalent C₂-C₄-alcohols, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, ethylhexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, cetyl (meth)acrylate, palmityl (meth)acrylate and stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate;
- (b) amides of monoethylenically unsaturated C₃-C₆-carboxylic acids, especially acrylic acid and methacrylic acid, with C₁-C₁₂-alkylamines and di(C₁-C₄-alkyl)amines, such as N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-tert-octyl(meth)acrylamide and N-undecyl(meth)acrylamide, and (meth)acrylamide;
- (c) vinyl esters of saturated C₂-C₃₀-carboxylic acids, in particular C₂-C₁₄-carboxylic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate;
- (d) vinyl C₁-C₃₀-alkyl ethers, in particular vinyl C₁-C₁₈-alkyl ethers, such as vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl 2-ethylhexyl ether and vinyl octadecyl ether;
- (e) N-vinylamides and N-vinyllactams, such as N-vinylformamide, N-vinyl-N-methyl-formamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylimidazol, N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam;
- (f) aliphatic and aromatic olefins, such as ethylene, propylene, C₄-C₂₄-α-olefins, in particular C₄-C₁₆-α-olefins, e.g. butylene, isobutylene, diisobutene, styrene and α-methylstyrene, and also diolefins with an active double bond, e.g. butadiene;
- (g) unsaturated nitriles, such as acrylonitrile and methacrylonitrile.

A preferred monomer D is selected from methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylamide, vinyl acetate, vinyl propionate, vinyl methyl ether, N-vinylformamide, N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam. N-vinylimidazol is particularly preferred.
If the monomer D is present in the copolymer of the present disclosure, then the proportion of monomer D may be up to 40%, preferably from 1% to 30%, more preferably from 5% to 20% by weight of the copolymer.
Preferred copolymers of the present disclosure include:
wherein indices y and z are such that the monomer ratio (z:y) is from 3:1 to 20:1 and the indices x and z are such that the monomer ratio (z:x) is from 1.5:1 to 20:1, and the polymer has a weight average molecular weight of from 20,000 to 500,000 g/mol, preferably from greater than 25,000 to 150,000 g/mol and especially from 30,000 to 80,000 g/mol.
The copolymers according to the present disclosure can be prepared by free-radical polymerization of the Monomers A and B and if desired C and/or D. The free-radical polymerization of the monomers can be carried out in accordance with all known methods, preference being given to the processes of solution polymerization and of emulsion polymerization. Suitable polymerization initiators are compounds which decompose thermally or photochemically (photoinitiators) to form free radicals, such as benzophenone, acetophenone, benzoin ether, benzyl dialkyl ketones and derivatives thereof.
The polymerization initiators are used according to the requirements of the material to be polymerized, usually in amounts of from 0.01% to 15%, preferably 0.5% to 5% by weight based on the monomers to be polymerized, and can be used individually or in combination with one another.
Instead of a quaternized Monomer B, it is also possible to use the corresponding tertiary amines. In this case, the quaternization is carried out after the polymerization by reacting the resulting copolymer with alkylating agents, such as alkyl halides, dialkyl sulfates and dialkyl carbonates, or benzyl halides, such as benzyl chloride. Examples of suitable alkylating agents which may be mentioned are, methyl chloride, bromide and iodide, ethyl chloride and bromide, dimethyl sulfate, diethyl sulfate, dimethyl carbonate and diethyl carbonate.
The anionic monomer C can be used in the polymerization either in the form of the free acids or in a form partially or completely neutralized with bases. Specific examples that may be listed are: sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium hydrogen carbonate, ethanolamine, diethanolamine and triethanolamine.
To limit the molar masses of the copolymers according to the present disclosure, customary regulators can be added during the polymerization, e.g. mercapto compounds, such as mercaptoethanol, thioglycolic acid and sodium disulfite. Suitable amounts of regulator are 0.1% to 5% by weight based on the monomers to be polymerized.
I. Quaternary Compound
The liquid hard surface cleaning composition may comprise a quaternary compound. Preferably, the liquid hard surface cleaning composition comprises the quaternary compound at a level of from 0.001 to 2% wt %, more preferably from 0.002 to 0.5 wt %, most preferably from 0.005 wt % to 01 wt % of the composition.
Traditionally, compositions comprising quaternary compounds tend to leave unsightly filming and/or streaking on the treated surfaces. However, compositions as presently disclosed surprisingly provide improved shine and reduced streaking. Without being bound to theory this improved shine benefit is a result of the dewetting property of the solvent. Furthermore, the compositions disclosed provide high antibacterial benefit delivering 5 logs micro efficacy while still delivering high shine.
Quaternary compounds useful herein are preferably selected from the group consisting of C₆-C₁₈alkyltrimethylammonium chlorides, C₆-C₁₈dialkyldimethylammonium chlorides, and mixtures thereof. Preferably, the quaternary compound is selected from the group consisting of a C₈-C₁₂alkyltrimethylammonium chloride, a C₈-C₁₂dialkyldimethylammonium chloride, and mixtures thereof. Most preferably, the quaternary compound is C₁₀dialkyldimethylammonium chloride.
Non-limiting examples of useful quaternary compounds include: (1) Maquat® (available from Mason), and Hyamine® (available from Lonza); (2) di(C₆-C₁₄)alkyl di short chain (C_1-4alkyl and/or hydroxyalkl) quaternary such as Uniquat® and Bardac® products of Lonza, (3)N-(3-chloroallyl) hexaminium chlorides such as Dowicil® and Dowicil® available from Dow; and (4) di(C₈-C₁₂)dialkyl dimethyl ammonium chloride, such as didecyldimethylammonium chloride (Bardac 22, Uniquat 2250 or Bardac 2250), and dioctyldimethylammonium chloride (Bardac 2050).
The quaternary compounds preferably are not benzyl quats. An example of such benzyl quat includes alkyl dimethyl benzyl ammonium chloride (Uniquat QAC).
J. Nitrogen-Containing Polymer
The liquid hard surface cleaning composition may comprise a nitrogen-containing polymer. Nitrogen-containing polymers useful herein include polymers that contain amines (primary, secondary, and tertiary), amine-N-oxide, amides, urethanes, and/or quaternary ammonium groups. When present, it is important that the polymers herein contain nitrogen-containing groups that tend to strongly interact with the surface being treated in order to displace any present cationic quaternary compound from the surface.
Preferably, the polymers herein contain basic nitrogen groups. Basic nitrogen groups include primary, secondary, and tertiary amines capable of acting as proton acceptors. Thus, the preferred polymers herein can be nonionic or cationic, depending upon the pH of the solution. Polymers useful herein can include other functional groups, in addition to nitrogen groups. The preferred polymers herein are also essentially free of, or free of, quaternary ammonium groups.
Preferably, the polymers herein are branched polymers, especially highly branched polymers including comb, graft, starburst, and dendritic structures. Preferably, the polymers herein are not linear polymers.
The nitrogen-containing polymers herein can be an unmodified or modified polyamine, especially an unmodified or modified polyalkyleneimine. Preferably, the nitrogen containing polymers herein are modified polyamines. Poly(C₂-C₁₂alkyleneimines) include simple polyethyleneimines and polypropyleneimines as well as more complex polymers containing these polyamines. Polyethyleneimines are common commercial materials produced by polymerization of aziridine or reaction of (di)amines with alkylenedichlorides. Polypropyleneimines are also included herein.
Although modified polyamines are preferred, linear or branched polyalkyleneimines, especially polyethyleneimines or polypropyleneimines, can be suitable in the present compositions to mitigate filming and/or streaking resulting from such compositions containing quaternary compounds. Branched polyalkyleneimines are preferred to linear polyalkyleneimines. Suitable polyalkyleneimines typically have a molecular weight of from about 1,000 to about 30,000 Daltons, and preferably from about 4,000 to about 25,000 Daltons. Such polyalkyleneimines are free of any ethoxylated and/or propoxylated groups, as it has been found that ethoxylation or propoxylation of polyalkyleneimines reduces or eliminates their ability to mitigate the filming and/or streaking problems caused by compositions containing quaternary compounds.
In preferred cleaning compositions typically comprise nitrogen-containing polymer at a level of from about 0.005% to about 1%, preferably from about 0.005% to about 0.3%, and more preferably from about 0.005% to about 0.1%, by weight of the composition.
Examples of preferred modified polyamines useful as nitrogen-containing polymers herein are branched polyethyleneimines with a molecular weight of about 25,000 Daltons, and Lupasol® FG, Lupasol® SK and Lupasol® SK(A) available from BASF.
K Additional Polymers
The liquid hard surface cleaning composition may comprise an additional polymer. It has been found that the presence of a specific polymer as described herein, when present, allows further improving the grease removal performance of the liquid composition due to the specific sudsing/foaming characteristics they provide to the composition. Suitable polymers for use herein are disclosed in co-pending EP patent application EP2272942 (09164872.5) and granted European patent EP2025743 (07113156.9).
The polymer can be selected from the group consisting of: a vinylpyrrolidone homopolymer (PVP); a polyethyleneglycol dimethylether (DM-PEG); a vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers; a polystyrenesulphonate polymer (PSS); a poly vinyl pyridine-N-oxide (PVNO); a polyvinylpyrrolidone/vinylimidazole copolymer (PVP-VI); a polyvinylpyrrolidone/polyacrylic acid copolymer (PVP-AA); a polyvinylpyrrolidone/vinylacetate copolymer (PVP-VA); a polyacrylic polymer or polyacrylicmaleic copolymer; and a polyacrylic or polyacrylic maleic phosphono end group copolymer; and mixtures thereof.
Typically, the liquid hard surface cleaning composition may comprise from 0.001% to 1.0% by weight of the total composition of said polymer, preferably from 0.005% to 0.5%, more preferably from 0.01% to 0.05% and most preferably from 0.01% to 0.03%.
L. Perfumes
The cleaning composition comprises a perfume composition formulated in an effective amount such that it provides a desired scent characteristic and can be homogenously solubilized in the cleaning composition to deliver a consistent release profile. The perfume composition comprises at least 60% by weight of the perfume composition of Perfume Raw Materials (PRMs) having an average C log P value greater than 1.0. The perfume composition may be in an amount of at least 0.005%, from 0.005% to 3%, from 0.005% to 1%, from 0.006% to 0.4%, or different combinations of the upper and lower percentages described above or combinations of any integer in the ranges listed above by weight of the cleaning composition.
When the alkoxylated phenol is ethoxylated phenol, the perfume composition may comprise at least 8%, from 80% to 99.9%, from 80% to 95%, from 85% to 95%, by weight of the perfume composition of PRMs having an average C log P distribution greater than 2.0, at least 2.5, more preferably greater than 3.0, even more preferably greater than 3.5; preferably an average C log P distribution is from 2.5 to 6.0, more preferably from 3.5 to 6.0.
M. Other Optional Ingredients
The liquid hard surface cleaning compositions may comprise a variety of other optional ingredients depending on the technical benefit aimed for and the surface treated. Suitable optional ingredients for use herein include builders, other polymers, buffers, bactericides, hydrotropes, colorants, stabilizers, radical scavengers, abrasives, soil suspenders, brighteners, anti-dusting agents, dispersants, dye transfer inhibitors, pigments, silicones and/or dyes.
The cleaning composition can be made in any suitable manner known in the art. All of the ingredients can simply be mixed together. In certain embodiments, it may be desirable to make a concentrated mixture of ingredients such as a pre-mix and dilute by adding the same to an aqueous carrier before use. In another embodiment, the ethoxylated phenol may be dispersed in one vessel containing ingredients such as water and may contain additional ingredients such as surfactants, solvent and polymers. All materials are added until fully dispersed and visually dissolved. In a separate vessel, the solubilizing materials (surfactants and solvents, and in some embodiments may contain the ethoxylated phenol) and perfume are mixed until homogenous. The solution of solubilizing materials and perfume are then added to the first mixing vessel, and mixed until homogenous.
II. Cleaning Pad
The liquid hard surface cleaning composition may be used in combination with a cleaning pad of the present disclosure. The cleaning pad may be dry and may contact a surface wetted with a cleaning composition, or the cleaning pad may be pre-moistened. The cleaning pad may comprise one or more layers.
Referring to FIGS. 1A, 1B and 2, the cleaning pad 10 may comprise plural layers, to provide for absorption and storage of cleaning fluid and other liquids deposited on the target surface. The target surface will be described herein as a floor, although one of skill will recognize the invention is not so limited. The target surface can be any hard surface, such as a table or countertop, from which it is desired to absorb and retain liquids such as spill, cleaning solutions, etc.
The cleaning pad 10 may comprise a liquid pervious floor sheet 14 which contacts the floor during cleaning and preferably provides a desired coefficient of friction during cleaning. An absorbent core 16, preferably comprising an absorbent gelling material (“AGM”) 16A is disposed on, and optionally joined to an inwardly facing surface of the floor sheet 14. The floor sheet may have an absorbency of at least 30%, more preferably at least 35%. It is to be appreciated that if the cleaning pad is to be used to clean a surface other than a floor, the floor sheet may be the sheet that contacts the surface to be cleaned.
The floor sheet of the cleaning pad may have a thickness from about 1 mm to about 5 mm, more preferably about 1.5 mm to about 3.0 mm and most preferably about 1.2 mm.
A smoothing strip 12 may be disposed on the outwardly facing surface of the floor sheet 14. Optionally, a back sheet 18 may be joined to the core 16 opposite the floor sheet 14, to provide for attachment of the cleaning pad 10 to an implement 30. The back sheet 18 may have an outwardly facing surface with one or more attachment strips 20 to particularly facilitate attachment to an implement 30. The cleaning pad 10 may be generally planar and define an XY plane and associated X, Y axes. The Z axis is perpendicular thereto and generally vertical when the cleaning pad 10 is in use on a floor.
If desired, the core 16 may comprise AGM 16A to increase the absorbent capacity of the cleaning pad 10. The AGM 16A may be in the form of particles may be distributed within the cleaning pad 10 in such a manner to avoid rapid absorbency and absorb fluids slowly, to provide for the most effective use of the cleaning pad 10. The AGM 16A also entraps dirty liquid absorbed from the floor, preventing redeposition. If desired foam absorbent material or fibrous material may be incorporated into the core 16.
Examining the cleaning pad 10 in more detail, the cleaning pad 10 may comprise plural layers disposed in a laminate. The lowest, or downwardly facing outer layer, may comprise apertures to allow for transmission of liquid therethrough and to promote the scrubbing of the target surface. One, two or more core 16 layers may provide for storage of the liquids and may comprise the absorbent gelling materials. The cleaning pad 10 may have an absorbent capacity of at least 10, 15, or 20 grams of cleaning solution per gram of dry cleaning pad 10, as set forth in commonly assigned U.S. Pat. Nos. 6,003,191 and 6,601,261.
The optional top, or upwardly facing layer, is a back sheet 18, and may be liquid impervious in order to minimize loss of absorbed fluids and to protect the user's hand if the cleaning pad 10 is used without an implement 30. The top layer may further provide for releasable attachment of the cleaning pad 10 to a cleaning implement 30. The top layer may be made of a polyolefinic film, such as LDPE. A suitable back sheet 18 comprises a PE/PP film having a basis weight of 10 to 30 gsm.
Attached to the back sheet 18 may be one or more optional attachment strips 20. The attachment strips 20 may comprise adhesive, preferably pressure sensitive adhesive, or may loops for removable attachment to complementary hooks on an implement 30. Suitable loop attachment strips 20 may comprise a laminate of PE film and Nylon loops.
The back sheet 18 and floor sheet 14 may be peripherally joined, as is known in the art. This arrangement creates a pocket for securely holding the core 16. The core 16 may be juxtaposed with, and optionally joined to the respective inwardly facing surfaces of the floor sheet 14 and back sheet 18.
The core 16 may comprise a single layer or two or more layers. If plural layers are selected for the core 16, the width of the layers may decrease as the floor sheet 14 is approached, as shown. The core 16 may comprise airlaid cellulose and optionally polymer fiber, as available from Glatfelter of York, Pa. If two airlaid cellulose core 16 layers are selected, each layer of the core 16 may have a basis weight of at least about 75, 100, 125, 150, 175, 200, or 225 gsm and less than about 300 gsm.
Preferably each layer of the core 16 comprises AGM 16A. The AGM 16A may absorb at least 10, 15 or 20 times its own weight. The AGM 16A may be blown into the airlaid core 16 layer during manufacture as is known in the art. Suitable AGM 16A is available as Z3070G from Evonik of Essen, Germany. Arlaid material containing a gradient AGM 16A distribution is available from Glatfelter of York, Pa.
The gradient distribution AGM 16A may be achieved by using more than one forming head. For example, an airfelt/AGM 16A line may have three forming heads. The first head may distribute a relatively large amount of AGM 16A relative to the cellulose distributed from that head. The second forming head may distribute a less amount of AGM 16A relative to the cellulose base, with this mixture being laid onto top of the first AGM 16A/cellulose base. This pattern may be repeated using as many forming heads as desired. If desired the final forming head may distribute pure cellulose and no AGM 16A. Generally, the layer from each forming head does not intermix with adjacent layers. Adhesive bonding and/or thermal bonding may hold superposed layers in place and provide structural rigidity.
Suitable core 16 layers and a suitable apparatus and process for making one or more layers of a core 16 having a gradient AGM 16A distribution are found in U.S. Pat. No. 8,603,622 issued Dec. 10, 2013. The teachings of U.S. Pat. No. 8,603,622 are incorporated herein by reference at column 5, lines 8-14 for the teaching of a suitable core 16 layer and at FIGS. 3-4, with the accompanying discussion at column 16, line 41 to column 17, line 59 for the teaching of production devices suitable to make a core 16 layer for the present invention.
If two airlaid cellulose core 16 layers are selected, the lower core layer 16L, juxtaposed with the floor sheet 14, may comprise about 10 to 20 weight percent AGM 16A, with about 15 percent being found suitable. The upper core layer 16U, juxtaposed with the optional back sheet 18, if any, may comprise about 20 to about 30 weight percent AGM 16A, with about 25 percent being found suitable. The total core 16, with all layers thereof considered, may comprise 5 to 50 w %, or 10 to 45 w % AGM 16A, the amount and gradient distribution of AGM 16A being found helpful for the present invention. The percentage of AGM 16A, as described and claimed herein refers to the weight percentage of AGM 16A in that particular core 16 layer (16U or 16L), without regard to the floor sheet 14, back sheet 18, smoothing strip 12 or attachment strips 20.
Each core layer 16L, 16U and particularly the upper core layer 16U may be further stratified to provide greater absorbency benefit. The upper core layer 16U may have three strata, as formed. The strata may comprise 0, 25, and 50 weight percent, monotonically increasing as the back sheet 18, if any, is approached, to provide a gradient distribution.
Generally, it is desired that the upper core layer 16U comprise more AGM 16A, on both an absolute basis and a weight percentage basis than the lower core layer 16L. The arrangement provides the benefit that gel blocking in the lower core layer 16L does not prevent full absorption of liquid from the target surface and that liquids are transported upwardly and away from the floor sheet 14.
Any arrangement that provides more AGM 16A, preferably on an absolute basis or optionally on a weight percentage basis is suitable. Alternatively, either core 16 layer or a single core 16 layer may have increasing AGM 16A concentration in the Z direction.
Any such process, as is known in the art, or arrangement, which provides for increasing AGM 16A in the Z direction as the back sheet 18 is approached is herein considered an AGM 16A gradient. It is to be recognized that the AGM 16A gradient may be smooth, comprise one or more stepwise increments or any combination thereof.
The floor sheet 14 may comprise a discrete apertured nonwoven having a basis weight of about 20 to about 80 gsm and particularly about 28 to 60 gsm. The floor sheet 14 may be hydrophobic and made of synthetic fibers. A suitable floor sheet 14 is a 60 gsm PE/PP discrete apertured spunbond nonwoven available as SofSpan from Fitsea of Simpsonville, S.C. The floor sheet 14 may have a contact angle of 101 to 180 degrees with water.
The floor sheet 14 may comprise a smoothing strip 12. The smoothing strip 12 may have a width less than the floor sheet 14 and may comprise at least about 10, 20, 30, 40, 50, 60 or 70% of the floor sheet 14 width. The smoothing strip 12 may have a width of at least 10, 20, 30, 40, 50, 100, 150, 200, 250, mm and less than 70, 80, 100, 200 or 300 mm, with a width of 24 to 44 mm being suitable and a width of 34 mm being preferred.
The smoothing strip 12 may be hydrophilic. As used herein hydrophilic means having a contact angle of 0 to 100 degrees, as measured by the test method set forth herein. The smoothing strip 12 may particularly have a contact angle of 30 to 100 degrees and more particularly 55 to 90 degrees. The smoothing strip 12 may comprise at least 50% cellulosic content to be hydrophilic.
More particularly, a suitable smoothing strip 12 may comprise a laminate of cellulose fibers and synthetic fibers. Such a laminate is believed to be helpful in attaining the performance of the cleaning pads 10 described herein. The cellulose fiber lamina may be outwardly facing, to provide friction and absorbency on the floor. The synthetic fiber layer may be positioned on contacting relationship with the floor sheet 14 to provide integrity during use.
A 23 gsm tissue and 17 gsm polypropylene spunbond hydroentagled, sold as 40 gsm Genesis tissue by Suominen of Helsinki, Finland has been found to be a suitable smoothing strip 12. Another suitable smoothing strip 12 may comprise 28 gsm tissue and 17 gsm polypropylene spunbond hydroentagled, sold as 45 gsm Hydratexture tissue by Suominen.
The smoothing strip 12 may have a surface texture less than 0.5 mm, 0.4 mm or less than 0.3 mm and even be essentially 0 mm. Surface texture is measured as the peak to valley distance, independent of the smoothing strip 12 thickness. A surface texture of less than 0.5 mm is believed to minimize streaking during cleaning, particularly when the floor dries and more particularly when a dark floor dries.
B. Wipe
The cleaning pad may be in the form of a cleaning wipe. The cleaning wipe may be used as a pre-moistened cleaning wipe or a dry wipe for use with a cleaning composition.
If the cleaning wipe is pre-moistened, it is pre-moistened with a cleaning composition, as described in further detail above, which provides for cleaning of the target surface, such as a floor, but yet does not require a post-cleaning rinsing operation.
The cleaning wipe used in conjunction with this cleaning composition may comprise natural or synthetic fibers. The fibers may be hydrophilic, hydrophobic or a combination thereof, provided that the cleaning wipe is generally absorbent to hold, and express upon demand, the above described cleaning composition. In one embodiment, the cleaning wipe may comprise at least 50 weight percent or at least 70 weight percent cellulose fibers, such as air laid SSK fibers. If desired, the cleaning wipe may comprise plural layers to provide for scrubbing, liquid storage, and other particularized tasks for the cleaning operation.
A cleaning wipe may have a thickness from about 1 mm to about 5 mm, more preferably about 1.5 mm to about 3.0 mm and most preferably about 1.2 mm.
The cleaning wipe may be loaded with at least 1, 1.5 or 2 grams of the cleaning composition, as described above, per gram of dry substrate, but typically not more than 5 grams per gram.
Optionally, the cleaning wipe may further comprise a scrubbing strip. A scrubbing strip is a portion of the cleaning wipe which provides for more aggressive cleaning of the target surface. A suitable scrubbing strip may comprise a polyolefinic film, such as LDPE, and have outwardly extending perforations, etc. The scrubbing strip may be made and used according to commonly assigned U.S. Pat. Nos. 8,250,700; 8,407,848; D551,409 S and/or D614,408 S. A suitable pre-moistened cleaning wipe maybe made according to the teachings of commonly assigned U.S. Pat. No. 6,716,805; D614,408; D629,211 and/or D652,633.
III. Cleaning Implement
The cleaning pad 10 and cleaning composition may be used by hand or with a cleaning implement 30. Referring to FIG. 3, the cleaning implement 30 may comprise a plastic head 32 for holding the cleaning pad 10 and an elongate handle 34 connected thereto. The handle 34 may comprise a metal or plastic tube or solid rod.
The head 32 may have a downwardly facing surface, to which the cleaning pad 10 may be attached. The downwardly facing surface may be generally flat, or slightly convex. The head 32 may further have an upwardly facing surface. The upwardly facing surface may have a universal joint to facilitate connection of the elongate handle 34 to the head 32.
A hook and loop system may be used to attach the cleaning pad 10 directly to the bottom of the head. Alternatively, the upwardly facing surface may further comprise a mechanism, such as resilient grippers, for removably attaching the cleaning pad 10 to the implement 30. If grippers are used with the cleaning implement 30, the grippers may be made according to commonly assigned U.S. Pat. Nos. 6,305,046; 6,484,346; 6,651,290 and/or D487,173.
The cleaning implement may further comprise a reservoir for storage of the cleaning composition, a described in further detail above. The reservoir may be replaced when the cleaning composition is depleted and/or refilled as desired. The reservoir may be disposed on the head or the handle of the cleaning implement of the reservoir may be separate from the cleaning implement. The neck of the reservoir may be offset per commonly assigned U.S. Pat. No. 6,390,335. The reservoir may be in the form of a spray bottle.
The cleaning implement 30 may further comprise a pump for dispensing cleaning solution from the reservoir onto the target surface, such as a floor. The pump may be battery powered or operated by line voltage. Alternatively, the cleaning solution may be dispensed by gravity flow. The cleaning solution may be sprayed through one or more nozzles to provide for distribution of the cleaning solution onto the target surface in an efficacious pattern.
If a replaceable reservoir is utilized, the replaceable reservoir may be inverted to provide for gravity flow of the cleaning solution. Or the cleaning solution may be pumped to the dispensing nozzles. The reservoir may be a bottle, and may be made of plastic, such as a polyolefin. The cleaning implement 30 may have a sleeve (36), which removably receives the bottle, or other reservoir. The cleaning implement 30 may have a needle, optionally disposed in the sleeve (36) to receive the cleaning solution from the bottle. The bottle may have a needle pierceable membrane, complementary to the needle, and which is resealed to prevent undesired dripping of the cleaning solution during insertion and removal of the replaceable reservoir. Alternatively, or additionally, if desired, the implement 30 may also provide for steam to be delivered to the cleaning pad 10 and/or to the floor or other target surface.
A suitable reservoir of cleaning solution and fitment therefore may be made according to the teachings of commonly assigned U.S. Pat. Nos. 6,386,392, 7,172,099; D388,705; D484,804; D485,178. A suitable cleaning implement 30 may be made according to the teachings of commonly assigned U.S. Pat. Nos. 5,888,006; 5,960,508; 5,988,920; 6,045,622; 6,101,661; 6,142,750; 6,579,023; 6,601,261; 6,722,806; 6,766,552; D477,701 and/or D487,174. A steam implement 30 may be made according to the teachings of jointly assigned 2013/0319463.
Method of Cleaning a Surface
Cleaning pads, cleaning wipes, and cleaning implements using cleaning pads and cleaning wipes may be used along with a liquid hard surface cleaning refreshing composition having an alkoxylated phenol for controlled emulsification of perfumes for cleaning hard surfaces.
Preferably cleaning pads, cleaning wipes, and cleaning implements using cleaning pads and cleaning wipes may be used along with a liquid surface cleaning refreshing composition having at least 85% by weight of water, at least 0.0015% of by weight of alkoxylated phenol; and a perfume, wherein the perfume comprises at least 60% by weight of the Perfume Raw Materials having C log P greater than 1.0, are suitable for cleaning household surfaces.
For general cleaning, especially of floors, a preferred method of cleaning comprises the steps of: wetting a hard surface with a cleaning refreshing composition and removing the cleaning refreshing composition from the hard surface by wiping the hard surface with a cleaning pad or cleaning wipe of the present disclosure. The step of wetting the hard surface may involve spraying the hard surface with a liquid cleaning refreshing composition or contacting the hard surface with a pre-moistened wipe or cleaning pad to wet the hard surface. A cleaning implement comprising a pre-moistened or dry cleaning pad or cleaning wipe may also be used to wet and/or remove the cleaning refreshing composition from the hard surface.
Test Methods:
A) Shine Test for Floor Cleaning:
The shine test is done with soil mixture which consists of a mixture of consumer relevant soils such as oil, particulates, pet hair, sugar etc. The dark colored engineered hardwood flooring is soiled with the soil mixture and cleaned with the liquid hard surface cleaning composition(s) and a cleaning pad is wiped up and down for a total of six (6) times to cover the entire flooring, after letting them dry, results are analyzed by using grading scale described below.


	and PSU Scale Versus a
	Reference
Grading in absolute scale:	(average of 3 graders):

0 = as new /no streaks and/or film	0 = I see no difference
1 = very slight streaks and/or film	1 = I think there is difference
2 = slight streaks and/or film	2 = I am sure there is a
3 = slight to moderate streaks	slight difference
and/or film	3 = I am sure there is a
4 = moderate streaks and/or film	difference
5 = moderate/heavy streaks and/or film	4 = I am sure there is a big
6 = heavy streaks and/or film	difference

B) Measurement of Turbidity:
A turbidimeter is used to determine how well ingredients can solubilize and emulsify perfume. The method of measuring turbidity is described in detail in the following reference: Hach Company, 2009, 2013, “Hach 2100Q and 2100Q is User Manual.” This method of measurement determines quantitative values of turbidity by evaluating the ratio of a primary nephelometric light scatter signal to a transmitted light scatter signal. This particular method of evaluation provides values between 0-1000 NTU, where increasing NTU values indicate more turbid solutions. Thus, successful perfume emulsification will yield lower NTU values vs. unsuccessful perfume emulsification will yield higher NTU values. In between each test sample, water controls should be measured to ensure proper equipment operation.
C) Measurement of (Consumer Relevant) Panelist Perfume Intensity:
A perfume intensity panel is used to determine the perfume intensity of the cleaning compositions. The method uses trained panelist selected by their ability to discriminate perfume intensities in a 0 to 100 scale. Testing is run in glass rooms with dimensions 15 ft wide, 15 ft length and 8 ft height with aluminum floor, to further reduce the effect of residual scent and to provide a non-absorbent cleaning surface. The rooms are controlled at a temperature between 18 to 25° C.±1° C. or 65 to 78° F.±3° F. and a relative humidity is controlled between 40-65% RH±5% with 4 air changes per hour.
Panelists evaluate rooms in groups of 2-5 depending on the total number of panelists available with a minimum of 4 groups per test. Panelists evaluate the room scent intensity on a 0-100 scale at the predetermined intervals, for example initial to 4 hours. In order to increase the ability of the panelist to discriminate between treatments, inventive samples are compared with comparative samples or controls. The evaluations are averaged and graphed as intensity versus time.
D) Measurement of Perfume Longevity:
An olfactometer such as the Scentroid SC300 from IDES is used to determine the longevity of a perfume composition at its odor detection threshold (ODT) from the correlation of its perfume concentration in the fluid phase and its intensity and psychophysical curves perceived by trained person. The method of measuring the intensity of the fragrance, using a dynamic scale method, at concentrations higher than the ODT concentration is described in ASTM E544-99. Longevity is obtained from the combination of a first order concentration decay model and a non-lineal regression of the psychophysical curves using the Hill equation.
The method uses a first order space concentration decay model to determine the concentration of fragrance in a room or space from a dwell time after mopping at the weight fraction of perfume in the composition.
$C (t) = C_{0} e^{(\frac{- Q}{V} t)}$
where:

- C(t) is the concentration in the room of the perfume at a given time
- t is the dwell time after mopping
- V is the room volume
- Q is the room volumetric air flow rate, which can be estimated as V·ACH
- ACH is the number of air changes per hour
- C₀is the initial concentration in the room, which can be estimated as:

$C_{0} = \frac{w_{p^{P}} \cdot A \cdot ϕ}{MW \cdot V \frac{P}{R T}}$

- where:
  - w_pPis the weight fraction of perfume in the composition
  - A is the floor surface area
  - φ is the mass per area of juice delivered to the floor during mopping
  - MW is the molar average molecular weight of the perfume
  - P is standard pressure
  - R is the universal gas constant
  - T is standard temperature

The olfactometer is used to generate psychophysical curves that correlate intensity to concentration at various dilutions of a fragrance. The intensity data is then fitted using a Hill equation nonlinear regression.
$I = \frac{β_{2} C^{β_{0}}}{β_{1}^{β_{0}} + C^{β_{0}}}$
where:

- I is the intensity
- β₀, β₁, β₂are fit parameters
- C is the vapor phase concentration.

The longevity of a perfume concentrations is estimated from the combination of the space concentration decay model, e.g. the weight fraction of the perfume in the fluid phase, and the transformed intensity at the odor detection threshold.
E) pH Measurement:
The pH is measured on the neat composition, at 25° C., using a Sartarius PT-10P pH meter with gel-filled probe (such as the Toledo probe, part number 52 000 100), calibrated according to the instructions manual.
F) Gas Chromatography/Flame Ionization Detector (GC/FID):
Distribution of ethoxylates in the comparative ethoxylated phenol samples and inventive ethoxylated phenol samples are analyzed by gas chromatography with mass selection detection and flame ionization detection (GC MSD/FID) and the distribution is expressed as a normalized FID area % for each sample.
The samples are prepared and analyzed according to the following steps:

- i) 13.0 (±1.0) mg of a sample for each ethoxylated phenol is added to 1 mL of 1 mL of methylene chloride into the GC vial.
- ii) The vial is capped and heated at 90+/−2 C for 15 mins.
- iii) The samples are analyzed by gas chromatography with flame ionization detection (GC/FID) under the following conditions:
  - Capillary GC Column: DB-1HT 5 m×0.25 mm ID, 0.1 μm film
  - Oven Program: 50 C (0 min)-25 C/min-395 C (10 min), Total 23.8 min
  - Column Flow: 1.0 ml/min (He), Average Velocity 34 cm/sec Injection Temp: 365 C, Sample Amount 1 μl, Split Ratio: 50:1
  - FID Temp: 400 C, H2 Flow: 40 ml/min, Air Flow 450 mL/min
- iv) Chromatograms are reprocessed integrating the area under only the phenyl ethoxylate peaks. Weight % is calculated by dividing the corresponding area under the curve for each phenyl ethoxylate peak by the summation of all phenyl ethoxylate areas.

Examples

TABLE 3

Perfume Composition Examples 1-3

Perfume Raw	Perfume	Perfume	Perfume
Material (PRM)	Composition 1	Composition 2	Composition 3

	Average ClogP	2.9	3.8	4.0
1	Ethyl Maltol	3	1.5	1
2	Helional	9	3	2
3	HYDROXY-	8	3	2
	CITRONELLAL
4	Ethyl Vanillin	3	1.5	1
5	Pyranol	8	3	2
6	Benzyl acetate	8	3	2
7	Methyl Phenyl	8	3	2
	Carbinyl Acetate
8	Ligustral Or	8	3	2
	Triplal
9	Linalool	8	3	2
10	Cyclo Galbanate	9	3	2
11	UN-	2	7	8
	DECALACTONE
12	Citronellol	8	3	2
13	LINALYL	2	7	8
	ACETATE
14	Verdox	2	7	8
15	4-tertiary-Butyl	2	7	8
	cyclohexyl acetate
16	Orange Terpenes	2	7	8
17	Ethyl	2	7	8
	Trimethyl-
	cyclopenteene
	Butenol

18	Ionone Gamma	2	7	8
	Methyl
19	Hexyl salicylate	2	7	8
20	Habanolide 100%	2	7	8
21	Iso E super	2	7	8
	Total weight	100	100	100
	of the perfume
	composition

TABLE 4

Ex Cleaning Freshness Compositions and Shine

Ex

4	Ex 5	Ex 6	Ex 7	Ex 8	Ex 9	Ex 10
	Wt %	Wt %	Wt %	Wt %	Wt %	Wt %	Wt %

Ethylene Glycol	0.6
Phenyl Ether
Diethylene Glycol		0.6
Phenyl Ether
Polyethylene Glycol			0.6				0.6
Phenyl Ether¹
Poly (octa) ethylene				0.6
Glycol Phenyl Ether²
Poly (deca) ethylene					0.6
Glycol Phenyl Ether²
Poly (pentadeca)						0.6
ethylene Glycol³
Phenyl Ether
Propylene glycol n-butyl ether	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Propylene Glycol	0.4	0.4	0.4	0.4	0.4	0.4	0.4
Phenyl Ether
Amine Oxide	0.05	0.05	0.05	0.05	0.05
Planteren APG						0.05	0.05
Didecyl	0.01	0.01	0.01	0.01	0.01	0.01	0.01
Dimethylammoium
Chloride
Perfume Composition
1	0.15	0.15	0.15	0.15	0.15	0.15	0.15
Hydrogenated,	0.4	0.4	0.4	0.4	0.4	0.4	0.4
Ethoxylated Castor
Oil
Minors and Water	to 100%	to 100%	to 100%	to 100%	to 100%	to 100%	to 100%
Shine Result	3.5	3.0	1.5	1.0	1.0	3.5	2.0
(absolute)
Shine Result (PSU)	−2.0	−1.5	Reference	+0.5	+0.5	−2.0	−0.5
ClogP	2.9	2.9	2.9	2.9	2.9	2.9	2.9
NTU	400	200	40	20	30	200	60
Appearance	Turbid	Turbid	Clear	Clear	Clear	Turbid	Clear
Stability	Fail	Fail	Pass	Pass	Pass	Fail	Pass

1. The polyethylene glycol phenyl ether is DOWANOL EPh6 Glycol Ether available from Dow.
2. The Poly (octa) ethylene glycol phenol ether and Poly (deca) ethylene glycol phenol ether are P&G Lab made samples.
3. The Poly (pentadeca) ethylene glycol phenol ether is a Dow Lab made sample.

Table 4 EX 6, surprisingly illustrates the benefit of polyethylene glycol phenylether (Example 6) over polyethylene glycol phenyl ether and diethylene glycol phenylether (Examples 4 & 5) in cleaning, clarity and stability. In addition, shows similar benefits for Poly (octa) ethylene glycol phenol ether and Poly (deca) ethylene glycol phenol ether, P&G lab made samples.
Table 5 shows Cleaning and Freshness compositions and and their benefits with respect to Scent Longevity


Ex 11	Ex 12	Ex 13	Ex 14	Ex 15	Ex 16	Ex 17	Ex 18
Wt %	Wt %	Wt %	Wt %	Wt %	Wt %	Wt %	Wt %

Polyethylene Glycol		0.6	0.4	0.9	0.9	0.9	0.9	0.4
Phenyl Ether¹
Propylene glycol n-butyl ether	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Propylene Glycol	0.4	0.4	0.4	0.4	0.4	0.9	0.9	0.9
Phenyl Ether¹
Amine Oxide	0.05	0.05	0.05	0.05	0.05	0.05	0.05	0.05
Didecyl	0.01	0.01	0.01	0.01	0.01			0.01
Dimethylammonium
Chloride
Perfume	0.04	0.15	0.10					0.10
Composition 1
Perfume				0.15	0.10
Composition 2
Perfume						0.15	0.10
Composition 3
Mirapol 300	0.01	0.01	0.01	0.01	0.01			0.01
Copolyner
Lupasol SK						0.02	0.02
Hydrogenated,		0.08	0.04	0.08	0.04	0.08	0.04
Ethoxylated Castor
Oil
Ethoxylated Castor								0.4
Oil
EtOH	0.2		0.2					0.2
Minors and Water	to 100%	to 100%	to 100%	to 100%	to 100%	to 100%	to 100%	to 100%
Shine Result	1.0	1.5	1.0	1.5	1.5	2.0	1.5	1.5
(absolute)
Shine Result (PSU)	+0.5	reference	+0.5	−0.5	+0.5	−0.5	+0.5	−0.5
ClogP	2.9	2.9	2.9	3.8	3.8	4.0	4.0	2.9
NTU	10	40	20	50	20	55	50	60
Longevity (min)	35	200	150	240	180	260	200	100
	Fail	Pass	Pass	Pass	Pass	Pass	Pass	Pass

1. The polyethylene glycol phenyl ether is DOWANOL EPh6 Glycol Ether available from Dow Chemical company.

As shown in Table 5, the preferred compositions formulated with polyethylene glycol phenyl ether (Examples 11-17) surprisingly are clear and stable composition with a significant benefit in perfume longevity over formulations without polyethylene glycol phenyl ether (Example 10).
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.
Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present disclosure have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A liquid hard surface cleaning composition comprising:

at least 85% by weight of water,

at least 0.0015% of by weight of alkoxylated phenol;

and a perfume,

wherein the perfume comprises at least 60% by weight of the Perfume Raw Materials having C log P greater than 1.0, wherein the composition has a Shine Result of between 0.1 and 2.0 and an NTU of between 1 and 200.

2. The composition of claim 1, wherein the alkoxylated phenol is selected from the group consisting of: a propoxylated phenol, an ethoxylated phenol, an ethoxylated-propoxylated phenol and combinations thereof, preferably an ethoxylated phenol.

3. The composition of claim 2, wherein ethoxylated phenol may be in an amount of at least 0.0015%, preferably from 0.0015% to 9%, 0.0015% to 3.5%, more preferably, 0.0015% to 2%, even more preferably 0.0015% to 1.5%, by weight of the cleaning composition.

4. The composition of claim 1, wherein said ethoxylated phenol is according to Formula 1:

wherein n is selected from 0 to 15, preferably 5 to 9, preferably from 4 to 8, more preferably from 5 to 7;

preferably n is an average value of from 3 to 10, preferably from 4 to 8, more preferably from 5 to 7.

5. The composition according to claim 1, wherein at least 80%, preferably 80 to 99.9%, more preferably from 80 to 95%, even more preferably from 85 to 95%, by weight of the perfume of perfume raw materials having C log P greater than 2.0, preferably at least 2.5, more preferably greater than 3.0, even more preferably greater than 3.5; preferably an average C log P distribution is from 2.5 to 6.0, more preferably from 3.5 to 6.0.

6. The composition according to claim 1, wherein the perfume is in an amount of at least 0.005%, preferably from 0.005% to 3%, more preferably from 0.005% to 1%, even more preferably from 0.006% to 0.4%, by weight of the cleaning composition.

7. The composition according to claim 1, wherein the PRMs having C log P greater than 1.0 are selected from the group consisting of: dihydro myrcenol, isononyl alcohol, citronellol, tetrahydro linalool, terpinyl acetate, geranyl acetate, phenyl ethyl phenyl acetate, lilial (P.T. Bucinal), Gamma methyl ionone, vertenex, diphenyl methane, p'cymene, alpha pinene, benzyl salicylate, d-limonene, cis-hexenyl salicylate, hexyl cinnamic aldehyde, cedryl acetate, habanolide, ethyl trimethylcyclopentene butanol, hexyl salicylate, iso e super, ethyl vanillin, helional, undecalactone, ionone gamma methyl, hydroxycitronellal, cyclo galbanate, pyranol, verdox, linalyl acetate, benzyl acetate, methyl phenyl carbinyl acetate, triplal, and mixtures thereof.

8. The composition according to claim 1, further comprising less than 3.5%, preferably from 0.01% to 3%, more preferably from 0.05% to 1%, even more preferably from 0.01% to 0.05% of a solubilizing aid by weight of the cleaning composition; preferably the solubilizing aid is selected from the group consisting of: a surfactant, a solvent and mixtures thereof, preferably the surfactant is selected from the group consisting of: nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof; preferably the solvent is selected from a group consistent of an alcohol, a polyol and mixtures thereof, more preferably the alcohol is ethanol.

9. The composition of claim 1, wherein the alkoxylated phenol is in an amount of at least 0.0015%, preferably from 0.0015% to 3.5%, more preferably, 0.0015% to 2%, even more preferably 0.0015% to 1.5%, by weight of the cleaning composition.

10. The composition according to claim 1, wherein the water is in an amount from 85% to 99.5%, preferably 90% to 99.5%, more preferably 95% to 99.5%, even more preferably 95%, by weight of the cleaning composition.

11. A method of improving shine of a hard surface, comprising the steps of:

a. wetting the hard surface with the cleaning composition of claim 1 and

b. removing the cleaning composition from the hard surface with a disposable dry cleaning wipe.

12. A disposable premoistened pad for cleaning hard surfaces comprising:

a substrate and

a liquid hard surface cleaning composition according to claim 1,

wherein said substrate is impregnated with said cleaning composition.